Dyes and methods of preparing them

ABSTRACT

The present writing relates to a novel fiber-reactive dye of the formula  
                 
 
     wherein R 11 , D, R 0 , X and Z are as defined in the specification. The novel dye according to the present writing can be used in dyeing and printing fibre materials, especially, cellulosic fibre materials by a general fixing method, and a good adsorbing/fixing rate and an excellent fastness to light and wet treatment.

TECHNICAL FIELD

[0001] The present writing relates to fiber-reactive dyes, which havetwo heterogeneous monoazo dye radical moieties in the chemical structurethereof, and methods of preparing them.

BACKGROUND

[0002] Fiber-reactive dyes with two monoazo dye radical moieties in themolecular structure have been disclosed in U.S. Pat. No. 5,484,899 andU.S. Pat. No. 5,548,071.

[0003] The dyes according to the present writing are distinguished by anexcellent fixing capacity and good wet- and light-fastness properties.Accordingly, the dyes according to this writing can solve problemsoccurring upon dying fibre materials at a high concentration with C.I.Reactive Red 120 compound and C.I. Reactive Yellow 84 compound, beingmonochlorotriazine-based reactive dyes, and with C.I. Reactive Red 195compound and C.I. Reactive Yellow 145 compound, being difunctionalreactive dyes, of which the structures are illustrated below,respectively.

[0004] In recent, more advanced methods are required to dye fibrematerials with reactive dyes in view of the quality of dyed goods and ofthe efficiency of dying process, which needs novel reactive dyes thathave a sufficient direct-dyeing property in the dyeing process and, ifnot fixed on fiber, can be easily washed. Accordingly, the novelreactive dyes are strongly required that also have an excellent fastnessto light, laundering, etc. while satisfying the above requirements.

[0005] Therefore, an object of the present invention is to providereactive dyes which have a high fixing capacity and a high fiber-dyebond stability and an excellent fastness property to light and water andin which a part of dyes, having been not fixed on a fiber, can be easilywashed. Furthermore, the reactive dyes in accordance with the presentinvention exhibit a significantly higher solubility than do thewell-known dyes in which two heterogeneously or homogeneously monoazomoieties are connected to each other in a backbone, thereby show a muchhigher reproducing property in the exhausting dyeing and continuousdyeing.

[0006] The inventors of the present writing, after having conductedextensive research and many experiments, found that novel dyes asdescribed in the formula 1 have a good build-up capacity as well as anexcellent fastness property to light and water laundering, and do notalmost leave non-fixed residual components due to an excellentadsorbing/fixing properties to have an advantage in wastewatertreatment, as compared with existing monochlorotriazine-based dyes andheterogeneous difunctional dyes. The dye described herein can be used indyeing and printing fibre materials, especially cellulosic fibrematerial by a general fixing method. The dye has a good absorbing/fixingrate and has excellent fastness to light and wet treatments (i.e. thedye exhibits excellent color fastness when exposed to light and/or wettreatments (e.g., with water)).

SUMMARY

[0007] The fiber-reactive dye of the present invention is as defined inthe formula

[0008] wherein,

[0009] R₁₁ is a lower alkyl group of C₁-C₄;

[0010] D is a monoazo chromophore moiety selected from the formulas 2a,2b, 2c, 3a and 3b defined as the below;

[0011]  in the formulas 2a to 2c,

[0012] a is 0 or 1;

[0013] b is 0 or 1;

[0014] c is 0 or 1;

[0015] d is 0 or 1;

[0016] e is 0 or 1;

[0017] f is 0 or 1;

[0018] 1 is the number 0 or 1;

[0019] R₁ and R₃ independently of one another are each hydrogen atom orC₁-C₄ alkyl group;

[0020] R₂ is sulfo, C₁-C₄ alkyl, C₁-C₄ alkylalkoxy or carboxyl group;

[0021] R₄ is sulfo, C₁-C₄ alkyl, C₁-C₄ alkylalkoxy, —NHCONH₂ or —NHCOTgroup, wherein T is methyl, ethyl, —CH₂CH₂COOH or —CH═CHCOOH group; and

[0022] J is vinyl or CH₂—CH₂—Q group, wherein Q is a leaving group whichcan be eliminable by a base:

[0023]  in the formulas 3a and 3b,

[0024] g is 0 or 1;

[0025] his 0 or 1;

[0026] R₅ is C₁-C₄ alkyl, C₁-C₄ alkoxy, hydroxyl, carbonyl, sulfo or—SO₂J group, wherein J is the same group as defined above;

[0027] R₆ is C₁-C₄ alkyl or carboxyl group;

[0028] R₇ and R₈ independently of one another are each C₁-C₄ alkylgroup; and

[0029] R₉ is hydrogen atom, carboamido, sulfomethyl, methylsulfonegroup;

[0030] R₀ is hydrogen atom or C₁-C₄ alkyl group, wherein the alkyl groupis substituted with halogen atom, hydroxyl, cyano, C₁-C₄ alkoxy, C₁-C₄alkoxy carbonyl, carbonyl or sulfo group, or unsubstituted;

[0031] X is a halogen atom, hydroxyl, cyanoamine,3-carboxypyridine-1-yl, 4-carboxypyridine-1-yl, 3-carbamoylpyridine-1-ylor an amine group optionally substituted with C₁-C₄ alkoxy or C₁-C₄alkyl group or unsubstituted, or X is an N-heterocyclic group in whichhetero atom(s) may be additionally contained; and

[0032] Z is the group of the formula 4 defined as the below.

[0033]  in the formula 4:

[0034] l is 0 or 1;

[0035] j is 0 or ;

[0036] k is 0 or 1;

[0037] R₁₀ is sulfo, C₁-C₄ alkyl, C₁-C₄ alkoxy or carboxyl group; and

[0038] J₁ is vinyl or CH₂—CH₂—Q group, wherein Q is a leaving groupwhich is eliminable by a base.

[0039] The fiber-reactive dye of the formula 1 according to the presentinvention has a higher reactivity, and a better fixing capacity and moreexcellent build-up capacity than do the existingmonochlorotriazine-based compounds and vinylsulfone-based compounds.

[0040] Preferably, R is hydrogen atom, B is an ethyl group, and X isfluoride or chloride atom.

[0041] Of compounds according to the formula 1, more preferablefiber-reactive dyes are the compounds defined as in the formulas 5 to 8below.

[0042] wherein

[0043] A is ammonia or C₁-C₃ alkyl group;

[0044] X₁ is fluoride or chloride atom; and

[0045] m is 0 or 1;

[0046] n is 0 or 1; and

[0047] o is 0 or 1;

[0048] wherein

[0049] 1 is the number 0 or 1;

[0050] p is 0 or 1;

[0051] q is 0 or 1;

[0052] r is 0 or 1;

[0053] s is 0 or 1;

[0054] R₂ is sulfo, C₁-C₄ alkyl, C₁-C₄ alkoxy or carboxyl group;

[0055] X₁ is fluoride or chloride atom; and

[0056] J is vinyl or CH₂—CH₂—Q group, wherein Q is a leaving group whichis eliminable by a base;

[0057] wherein

[0058] 1 is the number 0 or 1;

[0059] p is 0 or 1;

[0060] q is 0 or 1;

[0061] r is 0 or 1;

[0062] s is 0 or 1;

[0063] R₂ is sulfo, C₁-C₄ alkyl, C₁-C₄ alkoxy or carboxyl group;

[0064] X₁ is fluoride or chloride atom; and

[0065] J is vinyl or CH₂—CH₂—Q group, wherein Q is a leaving group whichis eliminable by a base;

[0066] wherein

[0067] t is 0 or 1;

[0068] u is 0 or 1;

[0069] R₈ is hydrogen atom or C₁-C₄ alkyl group, wherein the alkyl groupis substituted with halogen atom, hydroxyl, cyano, C₁-C₄ alkoxy, C₁-C₄alkoxycarbonyl, carbonyl, sulfo group, or unsubstituted;

[0070] R₉ is hydrogen atom, carboamide, sulfomethyl, methylsulfonegroup; and

[0071] X₁ is fluoride or chloride atom.

[0072] Methods of preparing the compounds of the formula 1 are describedbelow. Hereinafter, R₁₁, D, R₀, X and Z in the formulas 9 to 13 are thesame as in the formula 1, unless stated otherwise. For convenience ofexplanation, the formulas 9 to 13 are first illustrated.

[0073] in the formulas 12 and 13, D₁RN corresponds to D in the formula1, wherein D₁ is a monoazo chromophore moiety; R is a substituted orunsubstituted C₁-C₄ alkyl group.

[0074] The compound of the formula 13, which is substantially the sameas the dye defined in the formula 1, can be synthesized by one of threemethods as below. It is noted that D in the formula 1 is expressed asD₁RN in formula 13 for convenience of explanation.

[0075] A first method of preparing the compound of the formula 13comprises,

[0076] A-1) the compound of the formula 11 is condensed with thecompound of HNR—D₁, followed by being condensed with the compound of theformula 9, to yield to the compound of the formula 12; and

[0077] A-2) the compound of the formula 12 is coupled with a diazoniumsalt derived from the compound of H₂N—Z to yield the compound of theformula 13.

[0078] A second method of synthesizing the compound of the formula 13comprises,

[0079] B-1) the compound of the formula 9 is coupled with a diazoniumsalt derived from the compound of H₂N—Z to yield the compound of theformula 10; and

[0080] B-2) the compound of the formula 11 is condensed with thecompound of the formula 10, followed by being condensed with HNR—D₁, toyield the compound of the formula 13.

[0081] A third method of synthesizing the compound of the formula 13comprises,

[0082] C-1) the compound of the formula 11 is condensed with thecompound of the formula 9, followed by being condensed with the compoundof H₂N—Z to yield the compound of the formula 12; and

[0083] C-2) the compound of the formula 12 is coupled with a diazoniumsalt derived from the compound of H₂N—Z to yield the compound of theformula 13.

[0084] Diazotization/coupling reactions in the above methods can beperformed by diazotizing the compound of H₂N—Z with nitrous acid at−5°-15° C. and pH 0.5-2, then coupling a diazonium salt thus synthesizedwith the compound of the formula 12 or 9 at −5°-15° C. and pH 0.5-2 byan acid coupler in an aqueous medium.

[0085] Both condensation reactions in each of the above methods can beperformed in an organic medium, aqueous medium, or aqueous-organicmedium, and preferably performed under the presence of acid coupler inthe aqueous medium. Preferable examples of said acid coupler includecarbonate, bicarbonate or hydroxide of alkali metal, carbonate,bicarbonate or hydroxide of alkaline earth metal, alkali metal acetate,mixture of these, tertiary amine, etc. Preferable examples of saidalkali metal and alkaline earth metal include lithium, sodium,potassium, calcium, etc. and preferable examples of said tertiary amineinclude pyridine, triethylamine, quinoline, etc. The first condensationreaction is performed at −10°-40° C., more preferably at 0°-10° C. andpH 1.0-6.8.

[0086] The second condensation reaction is performed preferably underthe presence of acid coupler in an aqueous medium at 10°-70° C. and pH2.0-9.0, more preferably at 20°-60° C. and pH 2.0-8.0.

[0087] The present invention also provides a novel compound, as definedin the formula 9, which can be used as intermediate in the above methodsfor synthesizing the dye of the formula 1.

[0088] wherein

[0089] R₀ and R₁₁ is the same as in the formula 1, and preferably R₁₁ isan ethyl group.

[0090] The compounds of the formula 9 can be synthesized by thefollowing method: 2,4-diaminobenzene-1 sulfonic acid is acylated in No.4 amino group of two amine groups therein by a conventional way and thenNo. 2 amino group is substituted with C₁-C₄ haloalkylalcohol, followedby the resulting reactant being hydrolyzed by conventional manners toyield the compound of the formula 9.

[0091] The present invention furthermore provides a process for dyeingor printing cellulosic fibre materials with the dye of the formula 1.

[0092] The dye of the formula 1 according to the present invention issuitable for dyeing or printing all-round cellulosic fibre materials.Examples of these cellulosic fibre materials include the naturallyoccurring cellulosic fibres, such as cotton, linen and hemp, and pulpsand regenerated celluloses; of them, the cotton is particularlypreferable. The dye of the formula 1 is also suitable for dyeing orprinting cellulosic blend fibres, for example, cotton/polyester,cotton/nylon blend fibres.

[0093] For dyeing processes, the amounts in which reactive dyes, likethe dye of the formula 1, are used in the dyebaths can vary according tothe desired depth of shade. The dye according to the present inventioncan be used in the amount of 0.01 to 10% by weight, preferably 0.01 to6% by weight, based upon the dye goods.

[0094] The dye of the formula 1 according to the present invention isespecially suitable for the exhaustion method.

[0095] Dyeing by the exhaustion method is in general carried out in anaqueous medium at a liquor ration of 1:2 to 1:60, preferably 1:5 to1:20, and a temperature of 20 to 105° C., preferably 30 to 90° C., morepreferably 40 to 80° C.

[0096] The pad dyeing method is another suitable dyeing process for thepresent invention, wherein fabrics is generally picked-up in an aqueoussolution, saline solution, salt solution, etc. Herein, pick-up iscarried out at 20 to 150%, preferably 40 to 120%, more preferably 50 to100%, based upon the weight of fibre material to be dyed. If appropriatein some cases, the aqueous solution contains a fixing alkali metal salt,and the fibre material after pick-up is treated with the fixing alkalimetal salt. Preferable examples of said alkali metal salt include sodiumcarbonate, sodium bicarbonate, sodium hydroxide, disodium phosphate,trisodium phosphate, sodium borate, aqueous ammonia, sodiumtrichloroacetate, sodium silicate, or mixtures of these. Since alkalihydroxide and/or alkali carbonate is preferable, sodium hydroxide and/orsodium carbonate of them is more preferable.

[0097] Fixation can be also performed by steaming the picked-up fibrematerial at 100° to 120° C., particularly by action of heat, such assaturated steam. According to, so-called, cold pad-batch method, dyesare put into a padder together with alkali, then kept at a roomtemperature for several hours, e.g., 3 to 40 hours, to be fixed to thefibre material. After fixation, the dyeings or prints are rinsedthroughout, if appropriate, by adding a dispersing agent thereto.

[0098] The dyeings and prints produced by the present invention on fibrematerials have an excellent build-up capacity and levelness. Moreover,they have a high fixing capacity and the unfixed dyes can be easilyremoved by rinsing. Also, the difference between adsorbing and fixingcapacities, i.e., the loss of soap is low. Furthermore, they have a highdepth of shape, a high fibre/dye bond stability, and a goodlight-fastness and good wet-fastness properties, such as fastness towashing, sea water, cross-dyeing and perspiration, as well as a goodfastness to pleating and fastness to ironing.

BRIEF DESCRIPTION OF THE DRAWINGS

[0099]FIG. 1 is a graph of comparing the fixing rates of the dyesynthesized in Example 8 according to the present invention, the dyesynthesized in Example 24 according to the present invention, C.I.Reactive Red 120 dye, and C.I. Reactive Red 195 dye;

[0100]FIG. 2 is a graph of comparing the relative dyeing intensities ofthe dye synthesized in Example 8 according to the present invention, thedye synthesized in Example 24 according to the present invention, C.I.Reactive Red 120 dye, and C.I. Reactive Red 195 dye.

[0101]FIG. 3 is a graph of comparing the solubilities of the dye ofprior art (refer to the formula 14 as mentioned later) and the dye ofEXAMPLE 24 in the conditions of exhaustion dyeing and continuous dyeing.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0102] The present invention is described in more detail with referenceto the following examples. However, the scope of the present inventionis not limited to these.

EXAMPLE 1

[0103] 4-aminobenzene-1,3-disulfonic acid was diazotized in thecustomary manner and then coupled with 3-ureidoaminoaniline to yield amonoazo compound. To 1000 g of an aqueous solution in which 41.54 g ofthe monoazo compound thus prepared was dissolved, 19.32 g of cyanuricchloride was added, followed by the condensation reaction beingconducted at 5° C. and pH 5 for 3 hours. When the reaction was ended,23.26 g of 1-amino-3-(2-hydroxyethyl)aminobenzene-4-sulfonic acid wasadded, followed by the condensation reaction being conducted at 30° C.and pH 5 for 3 hours. To the reaction solution, 28.13 g of diazosolution of 4-sulfatoethylsulfone-1-aminobenzene was added, followed bythe coupling reaction being conducted at 10° C. and pH 5.5 for 3 hours.After non-dissolved components were removed from the resulting solutionby filtering, 105.14 g of the brown compound, as depicted in the belowformula, λ_(max)=421 nm, was obtained.

[0104] This compound dyed cellulosic fibres in yellow shades with a goodlight-fastness and washing-fastness properties. For confirmation of thefastness to washing, the below several dyeing processes were conducted.

Dyeing 1

[0105] 2 g of the dye compound as obtained above was dissolved in 400 gof water. To this solution, 1500 g of a solution containing 53 g ofsodium chloride per liter was added to prepare a dyebath. 100 g of acotton fabric was introduced in the dyebath at 40° C. and, after 45minutes, 100 g of a solution containing 16 g of sodium hydroxide and 20g of anhydrous sodium carbonate per liter was added thereto. The dyebathwas kept at 40° C. for 45 minutes. Thereafter, the dyed fabric wasrinsed, soaped at the boil with a nonionic detergent for 25 minutes,rinsed again, and subsequently dried.

Dyeing 2

[0106] 2 g of the dye compound as obtained above was dissolved in 400 gof water. To this solution, 1500 g of a solution containing 53 g ofsodium chloride per liter was added to prepare a dyebath. 100 g of acotton fabric was introduced in the dyebath at 35° C. and, after 20minutes, 100 g of a solution containing 16 g of sodium hydroxide and 20g of anhydrous sodium carbonate per liter was added thereto. The dyebathwas kept at 35° C. for 15 minutes, then heated to 60° C. in the courseof 20 minutes and kept at this temperature for a further 35 minutes.Thereafter, the dyed fabric was rinsed, soaped at the boil with anonionic detergent for 25 minutes, rinsed again, and subsequently dried.

Printing

[0107] 3 g of the dye compound as obtained above was sprinkled, whilestirring rapidly, into 100 g of a stock thickener comprising 50 g ofsodium alginate thickener, 27.8 g of water, 20 g of urea and 1.2 g ofsodium m-nitrobenzenesulfonate. A cotton fabric was printed with theprinting paste thus prepared. The printed fabric was steamed at 102° C.in saturated steam for 2 minutes and then rinsed, if appropriate soapedat the boil and rinsed again, and subsequently dried.

EXAMPLE 2

[0108] 4-aminobenzene-1,3-disulfonic acid was diazotized in thecustomary manner and then coupled with 3-ureidoaminoaniline to yield amonoazo compound. To 1000 g of an aqueous solution in which 41.54 g ofthe monoazo compound prepared thus was dissolved, 13.91 g of cyanuricfluoride was added, followed by the condensation reaction beingconducted at 0° C. and pH 5 for 3 hours. When the reaction was ended,23.26 g of 1-amino-3(2-hydroxyethyl)aminobenzene-4-sulfonic acid wasadded, followed by the condensation reaction being conducted at 30° C.and pH 5 for 3 hours. To the reaction solution, a diazonium saltsolution containing 28.13 g of 4-sulfatoethylsulfone-1-aminobenzene wasadded, followed by the coupling reaction being conducted at 10° C. andpH 5.5 for 3 hours. After non-dissolved components were removed from theresulting solution by filtering, 103.5 g of the brown compound, asdepicted in the below formula, λ_(max)=420 nm, was obtained.

[0109] This compound dyed cellulosic fibres in yellow shades with a goodlight-fastness and washing-fastness properties. For confirmation of thefastness to washing, the dyeing processes were conducted in the samemanner as in EXAMPLE 1.

EXAMPLE 3

[0110] 19.32 g of cyanuric chloride was suspended in an aqueous solutionbelow 0° C. for 30 minutes and a solution containing 23.93 g of6-amino-1-naphthol-3-sulfonic acid was added thereto. The resultingsolution was kept at pH 3 and 5° C. until the condensation reaction wascompleted.

[0111] 30.31 g of 2-amino-naphthol-1,5-disulfonic acid was diazotized inthe customary manner, then added to the above reaction solution toconduct the additional condensation reaction at pH 8 and 10° C.

[0112] To the resulting solution, 23.26 g of1-amino-3-(N-hydroxyethyl)aminobenzene-4-sulfonic acid was added, andthe reaction solution was kept at pH 5 and 50° C. for 3 hours tocomplete the reaction, followed by a diazonium salt corresponding to28.13 g of 4-sulfatoethylsulfon-1-aminobenzene being added thereto. Whenthe reaction was ended at pH 7 and 10° C., non-solved components wereremoved by filtering and then the reactant was dried. Subsequently, adeep brown compound of the below formula (λ_(max)=480 nm) was obtainedin an amount of 119 g.

[0113] This compound dyed cellulosic fibres in scarlet shades with agood light-fastness and washing-fastness properties. For confirmation ofthe fastness to washing, the dyeing processes were conducted in the samemanner as in EXAMPLE 1.

EXAMPLE 4

[0114] 28.13 g of 4-sulfatoethylsulfone-1-aminobenzen was diazotized inthe customary manner, and the diazonium salt solution thus prepared wasadded to a solution in which 23.26 g of1-amino-3-(N-hydroxyethyl)aminobenzen-4-sulfonic acid was dissolved as acoupling component to conduct the coupling reaction. To 100 g of thesolution in which 52.46 g of the monoazo compound obtained from theabove reaction was contained, 19.32 g of cyanuric chloride was added,then kept at pH 5 and 5° C. for 3 hours. When the reaction was ended,the aqueous solution containing 31.93 g of8-amino-1-naphthol-3,6-disulfonic acid was added to the reactionsolution, then kept at pH 5 and 30° C. for 3 hours. To this solution,the diazonium salt solution corresponding to 30.31 g of2-amino-naphthalene-1,5-disulfonic acid was added, then kept at pH 5.5and 10° C. for 3 hours to complete the reaction. Non-dissolved componentwere removed from the reaction solution by filtering and then theresultant was dried. Subsequently, a dark red compound of the belowformula (λ_(max)=514 nm) was obtained in an amount of 126.96 g.

[0115] This compound dyed cellulosic fibres in deep red shades with agood light-fastness and washing-fastness properties. For confirmation ofthe fastness to washing, the dyeing processes were conducted in the samemanner as in EXAMPLE 1.

EXAMPLES 5 TO 24

[0116] Similarly to the above EXAMPLES, the compounds (R₁₁═CH₂CH₂) asdescribed in TABLE 1 were synthesized. The methods for synthesizingthese compounds can be easily understood from the above EXAMPLES andtheir chemical structures by the persons skilled in the art, withoutdetailed description. These compounds were tested in the same manner asin EXAMPLE 1.

[0117] From the testing results, these compounds were to confirmed to bedyes which have a very good fiber-reactive property, and can dye orprint cellulosic fibre materials by the fixing method, generally used inthe field of fiber-reactive dye, and also have a good adsorbing/fixingrate and a very excellent fastness to light and wet treatment. TABLE 1EX- Color of AM- dyed PLE D (monoazo chromphore) X Z materials 5

Cl

Yellow 6

Cl

Yellow 7

Cl

Yellow 8

Cl

Yellow 9

F

Yellow 10

Yellow 11

Yellow 12

Cl

Yellow 13

Cl

Orange 14

Cl

Orange 15

Cl

Orange 16

F

Orange 17

F

Orange 18

F

Orange 19

Orange 20

Cl

Scarlet 21

Cl

Scarlet 22

F

Scarlet 23

F

Scarlet 24

Cl

Scarlet

COMPARATIVE EXAMPLES 1 & 2

[0118] The relative extent of dyeing was measured for cotton fabricsdyed with the dyes synthesized in EXAMPELS 8 and 24, C.I. ReactiveYellow 84 dye, C.I. Reactive Red 120 dye, C.I. Reactive Yellow 145 dyeand C.I. Reactive Red 195, respectively, in the same manner as inDYEING-1 in EXAMPLE 1. For this, the relative dyeing intensity wasmeasured using a color difference meter (Gretag Macbeth LLC.), and thefixing rates before dyeing and after dyeing were measured using a UVspectrometer (Agilent Technologies Inc.). The results are described inFIGS. 1 and 2, respectively.

[0119] As seen from FIGS. 1 and 2, the dyes of EXAMPLES 8 and 24according to the present invention were confirmed to exhibit a betterfixing rate and relative dyeing intensity than do C.I. Reactive Yellow84 dye, C.I. Reactive Red 120 dye, C.I. Reactive Yellow 145 dye and C.I.Reactive Red 195 dye.

COMPARATIVE EXAMPLE 3

[0120] Each solubility of the compound of the below formula 14, being awell-known dye in the relevant prior art, and the dye produced inEXAMPLE 24 was measured under the conditions of exhaustion dyeing andcontinuous dyeing, respectively. Specifically, the solubility in theexhaustion dyeing condition was measured as a maximum concentration ofboth dyes soluble in a solution containing sodium carbonate of 20 g/Land sodium sulfate of 50 g/L at 60° C. for 30 minutes. The solubility inthe continuous dyeing condition was measured as a maximum concentrationof both dyes soluble in a solution containing 25% sodium hydroxide of 26mL and sodium sulfate of 30 g/L at 30° C. for 120 minutes. The resultsare described in FIG. 3, respectively.

[0121] As seen from FIG. 3, the dye of EXAMPLE 24 according to thepresent invention was confirmed to exhibit a significant solubility thando the dye compound of the formula 14 as a known dye, in both exhaustiondyeing and continuous dyeing conditions.

[0122] The invention being thus described, it will be obvious that it issusceptible to obvious modifications and variations. Such variations arenot to be regarded as a departure from the spirit and scope of theinvention, and all such modifications as would be obvious to one skilledin the art were intended to be included within the scope of thefollowing claims.

[0123] The Applicant reserves the right to claim or disclaim now or inthe future any feature, combination of features, or subcombination offeatures that is disclosed herein.

[0124] All of the numerical and quantitative measurements set forth inthis application (including in the description, claims, abstract,drawings, and any appendices) are approximations.

[0125] The invention illustratively disclosed or claimed herein suitablymay be practiced in the absence of any element which is not specificallydisclosed or claimed herein. Thus, the invention may comprise, consistof, or consist essentially of the elements disclosed or claimed herein.

[0126] The following claims are entitled to the broadest possible scopeconsistent with this application. The claims shall not necessarily belimited to the preferred embodiments or to the embodiments shown in theexamples.

[0127] This patent application claims Convention priority to KoreanPatent Application No. 10-2002-0030331 (filed 30 May 2002), to KoreanPatent Application No. 10-2002-0030333 (filed 30 May 2002), and toKorean Patent Application No. 10-2002-0030398 (filed 30 May 2002). Theentire contents of Korean Patent Application Nos. 10 2002-0030331,10-2002-0030333, and 10-2002-0030398 are expressly incorporated hereinby this reference.

[0128] All patents, prior filed patent applications, and any otherdocuments and printed matter cited or referred to in this applicationare incorporated in their entirety herein by this reference.

What is claimed is:
 1. A fiber-reactive dye as defined in formula 1below:

wherein, R₁₁ is a lower alkyl group consisting of C₁-C₄; D is a monoazochromophore moiety as defined below in formula 2a, 2b, 2c, 3a, or 3b:

 wherein in the formulas 2a to 2c, a is 0 or 1; b is 0 or 1; c is 0 or1; d is 0 or 1; e is 0 or 1; f is 0 or 1; l is 0 or 1; R₁ and R₃independently of one another are each a hydrogen atom or a C₁-C₄ alkylgroup; each R₂ is independently a sulfo, C₁-C₄ alkyl, C₁-C₄ alkylalkoxy,or carboxyl group; each R₄ is independently a sulfo, C₁-C₄ alkyl, C₁-C₄alkylalkoxy, —NHCONH₂, or a —NHCOT group, wherein T is methyl, ethyl,—CH₂CH₂COOH, or a —CH═CHCOOH group; and J is vinyl or a CH₂—CH₂—Q group,wherein Q is a leaving group which can be eliminated by a base asdefined in the formula 3a or 3b below:

wherein in the formulas 3a and 3b, g is 0 or 1; h is 0 or 1; R₅ is aC₁-C₄ alkyl, C₁-C₄ alkoxy, hydroxyl, carbonyl, sulfo, or —SO₂J group,wherein J is defined above; R₆ is a C₁-C₄ alkyl or carboxyl group; R₇and R8 independently of one another are each a C₁-C₄ alkyl group; and R₉is a hydrogen atom, or a carboamido, sulfomethyl, or methylsulfonegroup; R₀ is a hydrogen atom or a C₁-C₄ alkyl group, wherein the alkylgroup is optionally substituted with a halogen atom, or R₀ is ahydroxyl, cyano, C₁-C₄ alkoxy, C₁-C₄ alkoxy carbonyl, carbonyl, or sulfogroup; X is a halogen atom or a hydroxyl, cyanoamine,3-carboxypyridine-1-yl, 4-carboxypyridine-1-yl, or3-carbamoylpyridine-1-yl group, or X is an amine group optionallysubstituted with a C₁-C₄ alkoxy or C₁-C₄ alkyl group, or X is anN-heterocyclic group in which hetero atom(s) may be additionallycontained; and Z is a group as defined in formula 4 below:

 wherein in the formula 4: i is 0 or 1; j is 0 or 1; k is 0 or 1; eachR₁₀ is independently a sulfo, C₁-C₄ alkyl, C₁-C₄ alkoxy, or carboxylgroup; and J₁ is vinyl or a CH₂—CH₂—Q group, wherein Q is defined above.2. The dye according to claim 1, wherein R₀ is a hydrogen atom, R₁₁ isan ethyl group, and X is a fluoride or chloride atom.
 3. The dyeaccording to claim 1, wherein the dye is one of the compounds defined informulas 5 to 8 below:

wherein in the formula 5: A is ammonia or a C₁-C₃ alkyl group; X₁ is afluoride or chloride atom; m is 0 to 1; n is 0 or 1; and o is 0 or 1;

wherein in the formula 6: l is 0 or 1; p is 0 or 1; q is 0 or 1; r is 0or 1; s is 0 or 1; each R₂ is independently a sulfo, C₁-C₄ alkyl, C₁-C₄alkoxy or carboxyl group; X₁ is a fluoride or chloride atom; and J isvinyl or a CH₂—CH₂—Q group, wherein Q is defined in claim 1;

wherein in the formula 7: l is 0 or 1; p is 0 or 1; q is 0 or 1; r is 0or 1; s is 0 or 1; each R₂ is independently a sulfo, C₁-C₄ alkyl, C₁-C₄alkoxy, or carboxyl group; X₁ is a fluoride or a chloride atom; and J isvinyl or a CH₂—CH₂—Q group, wherein Q is defined in claim 1;

wherein in the formula 8: t is 0 or 1; u is 0 or 1; R₈ is a hydrogenatom or a C₁-C₄ alkyl group, wherein the alkyl group is optionallysubstituted with a halogen atom, or a hydroxyl, cyano, C₁-C₄ alkoxy,C₁-C₄ alkoxycarbonyl, carbonyl, or sulfo group; R₉ is a hydrogen atom,or a carboamide, sulfomethyl, or methylsulfone group; and X₁ is afluoride or chloride atom.
 4. A method of preparing the dye of theformula 1 as claimed in claim 1, wherein the method is one of Methods(A), (B), and (C) as defined below: Method (A) comprises the followingsteps: A-1) a compound defined in formula 11 below is condensed with acompound defined by formula HNR—D₁, followed by being condensed with acompound defined in formula 9 below, to yield a compound defined informula 12 below; and A-2) the compound defined in the formula 12 iscoupled with a diazonium salt derived from a compound defined in formulaH₂N—Z to yield a compound defined in formula 13 below; Method (B)comprises the following steps: B-1) a compound defined in formula 9below is coupled with a diazonium salt derived from the compound of theformula H₂N—Z to yield a compound defined in formula 10 below; and B-2)the compound defined in the formula 11 is condensed with the compounddefined in the formula 10, followed by being condensed with HNR-D₁, toyield the compound defined in the formula 13; Method (C) comprises thefollowing steps: C-1) the compound defined in the formula 11 iscondensed with the compound defined in the formula 9, followed by beingcondensed with the compound defined in the formula H₂N—Z to yield thecompound defined in the formula 12; and C-2) the compound defined in theformula 12 is coupled with a diazonium salt derived from the compounddefined in the formula H₂N—Z to yield the compound defined in theformula 13; wherein the formula 9 is:

wherein the formula 10 is:

wherein the formula 11 is:

wherein the formula 12 is:

wherein the formula 13 is:

wherein R₁₁, D, R₀, X and Z are defined in claim 1; wherein D₁ is amonoazo chromophore moiety; wherein R is a substituted or unsubstitutedC₁-C₄ alkyl group; and wherein the D₁RN in the formula 13 corresponds toD in the formula 1 in claim
 1. 5. A compound defined in formula 9 below:

wherein R₀ is a hydrogen atom or a C₁-C₄ alkyl group, wherein the alkylgroup is optionally substituted with a halogen atom, or R₀ is ahydroxyl, cyano, C₁-C₄ alkoxy, C₁-C₄ alkoxy carbonyl, carbonyl, or sulfogroup; and wherein R₁₁ is a lower alkyl group of C₁-C₄.
 6. The compoundaccording to claim 5, wherein R₁₁ is an ethyl group.
 7. A method ofpreparing the compound as claimed in claim 6, wherein the amino group ofNo. 4 in 2,4-diaminobenzene-1 sulfonic acid is acylated, and the aminogroup of No. 2 is substituted with C₁-C₄ haloalkylalcohol, followed bybeing hydrolyzed.
 8. A process for dyeing and printing cellulosic fibrematerials, which comprises treating the fibre materials with the dyedefined in the formula 1 as claimed in claim 1.